阅读说明：本技术 石墨烯天然橡胶高分子冰上止滑混合发泡材料及其制备方法 (Graphene natural rubber polymer ice top-slip mixed foam material and preparation method thereof ) 是由 丁天宁 丁德材 丁幼丝 于 2019-10-14 设计创作，主要内容包括：本发明公开了一种石墨烯天然橡胶高分子冰上止滑混合发泡材料及其制备方法,由包括以下重量份的原料制成：天然橡胶50～60份、丁基橡胶32～37份、顺丁橡胶8～12份、白炭黑4～6份、玄武岩纤维2.4～2.8份、纳米二氧化硅2～3份、石墨烯2.2～2.6份、硅酮油1.4～1.7份、氧化锌1.2～1.5份、硬脂酸锌1.5～2.0份、硬脂酸1.8～2.4份、交联剂1.6～1.9份、流动助剂4.5～5.5份、发泡剂1.5～2.0份。本发明的石墨烯天然橡胶高分子冰上止滑混合发泡材料止滑系数高,止滑效果好；耐低温性能好,低温防滑效果好；拉伸强度高,力学性能好,磨耗低,耐磨性能好,使用寿命长。(The invention discloses a graphene natural rubber polymer ice top-slip mixed foaming material and a preparation method thereof, wherein the graphene natural rubber polymer ice top-slip mixed foaming material is prepared from the following raw materials in parts by weight: 50-60 parts of natural rubber, 32-37 parts of butyl rubber, 8-12 parts of butadiene rubber, 4-6 parts of white carbon black, 2.4-2.8 parts of basalt fiber, 2-3 parts of nano silicon dioxide, 2.2-2.6 parts of graphene, 1.4-1.7 parts of silicone oil, 1.2-1.5 parts of zinc oxide, 1.5-2.0 parts of zinc stearate, 1.8-2.4 parts of stearic acid, 1.6-1.9 parts of a cross-linking agent, 4.5-5.5 parts of a flow assistant and 1.5-2.0 parts of a foaming agent. The graphene natural rubber polymer ice top-slip mixed foaming material is high in slip resistance coefficient and good in slip resistance effect; the low temperature resistance is good, and the low temperature antiskid effect is good; high tensile strength, good mechanical property, low abrasion, good wear resistance and long service life.)

1. The graphene natural rubber polymer ice top-slip mixed foam material is characterized by being prepared from the following raw materials in parts by weight:

50-60 parts of natural rubber, 32-37 parts of butyl rubber, 8-12 parts of butadiene rubber, 4-6 parts of white carbon black, 2.4-2.8 parts of basalt fiber, 2-3 parts of nano silicon dioxide, 2.2-2.6 parts of graphene, 1.4-1.7 parts of silicone oil, 1.2-1.5 parts of zinc oxide, 1.5-2.0 parts of zinc stearate, 1.8-2.4 parts of stearic acid, 1.6-1.9 parts of a cross-linking agent, 4.5-5.5 parts of a flow assistant and 1.5-2.0 parts of a foaming agent; the graphene is a multilayer graphene microchip; the cross-linking agent is a mixture of sulfur, dicumyl peroxide and zinc dimethacrylate.

2. The graphene natural rubber polymer ice top-slip mixed foaming material according to claim 1, wherein the graphene natural rubber polymer ice top-slip mixed foaming material is prepared from the following raw materials in parts by weight: 55 parts of natural rubber, 35 parts of butyl rubber, 10 parts of butadiene rubber, 5 parts of white carbon black, 2.6 parts of basalt fiber, 2.5 parts of nano-silica, 2.4 parts of graphene, 1.5 parts of silicone oil, 1.3 parts of zinc oxide, 1.7 parts of zinc stearate, 2.1 parts of stearic acid, 1.7 parts of a cross-linking agent, 5 parts of a flow aid and 1.8 parts of a foaming agent.

3. The graphene natural rubber polymer ice top-slip mixed foam material according to claim 1, wherein the number of the multi-layer graphene nanoplatelets is 5-10.

4. The graphene natural rubber polymer ice top-slip mixed foam material according to claim 1, wherein the mass ratio of sulfur, dicumyl peroxide and zinc dimethacrylate in the mixture of sulfur, dicumyl peroxide and zinc dimethacrylate is 10: (5-7): (2-3).

5. The graphene natural rubber polymer ice top-slip mixed foaming material according to claim 1, wherein the white carbon black is silane coupling agent modified white carbon black.

6. The graphene natural rubber polymer ice top-slip mixed foaming material according to claim 5, wherein the silane coupling agent modified white carbon black is silane coupling agent KH570 modified white carbon black.

7. The graphene natural rubber polymer ice top-slip mixed foam material as claimed in claim 1, wherein the zinc oxide is active zinc oxide.

8. The graphene natural rubber polymer ice top-slip mixed foam material as claimed in claim 1, wherein the foaming agent is azodicarbonamide.

9. The graphene natural rubber polymer ice top-slip mixed foam material as claimed in claim 1, wherein the flow aid is polyethylene wax.

10. The preparation method of the graphene natural rubber polymer ice top-slip mixed foam material as claimed in any one of claims 1 to 9, which is characterized by comprising the following steps:

A. respectively weighing natural rubber, butyl rubber, butadiene rubber, white carbon black, basalt fiber, nano silicon dioxide, graphene, silicone oil, zinc oxide, zinc stearate, stearic acid, a cross-linking agent, a flow assistant and a foaming agent according to parts by weight;

B. feeding natural rubber into an internal mixer, masticating for 12-14 min at the temperature of 144-148 ℃, and discharging; storing the masticated natural rubber at room temperature for more than 48h for later use;

C. b, conveying the natural rubber subjected to the mastication treatment in the step B, butyl rubber, butadiene rubber, white carbon black, basalt fiber, nano silicon dioxide, graphene, silicone oil, zinc oxide, zinc stearate, stearic acid and a flow aid into an internal mixer, and internally mixing for 11-14 min at the temperature of 88-92 ℃; then banburying for 8-13 min under the condition that the temperature is 105-110 ℃; then adding a cross-linking agent and a foaming agent, banburying at 122-124 ℃ for 10-12 min, and discharging to obtain a banburying rubber mixture;

D. c, conveying the banburying rubber mixture obtained in the step C into an open mill, thinning for 2-4 times on the open mill, and discharging to obtain an open mill rubber mixture;

and finally, feeding the open-mill rubber mixture into a mold for hot-pressing foaming, cooling and molding, and cutting a sample to obtain the graphene natural rubber polymer ice top-slip mixed foaming material.

Technical Field

The invention relates to the technical field of rubber products, in particular to a graphene natural rubber polymer ice top-slip mixed foaming material and a preparation method thereof.

Background

Natural Rubber (NR) is a natural polymer compound containing cis-1, 4-polyisoprene as a main component, 91 to 94% of which is rubber hydrocarbon (cis-1, 4-polyisoprene), and the balance of which is non-rubber substances such as protein, fatty acid, ash, saccharides and the like. The material is generally a flaky solid, has the relative density of 0.94, the refractive index of 1.522 and the elastic modulus of 2-4 MPa, is softened at 130-140 ℃, is sticky and soft at 150-160 ℃, and begins to degrade at 200 ℃. Has high elasticity and slight plasticity at normal temperature and is crystallized and hardened at low temperature. Has better alkali resistance but does not resist strong acid. Is insoluble in water, lower ketones and alcohols, and can swell in nonpolar solvents such as chloroform, carbon tetrachloride, etc.

The natural rubber mainly has a macromolecular chain structure, the molecular weight, the distribution and aggregation structure of the molecular weight, the macromolecular chain structural unit of the natural rubber is isoprene, the macromolecular chain is mainly composed of polyisoolefine, the content of the rubber accounts for more than ninety-seven percent, aldehyde groups are arranged on the molecular chain, one aldehyde group is arranged on each macromolecular chain on average, just condensation or reaction with a protein decomposition product is carried out on the aldehyde groups to form branching and crosslinking, so that the viscosity of the rubber in storage is increased, and epoxy groups are arranged on the macromolecular chains of the natural rubber and are more active. The macromolecule end of the natural rubber is generally inferred to be dimethylallyl, the other end of the natural rubber is pyrophosphate, a terminal group, aldehyde group of a molecular chain and polymeric elements are few, the molecular weight range of the natural rubber is wide in the aspects of the molecular weight and the distribution of the molecular weight, the vast majority of the molecular weight is about thirty thousand according to the report from abroad, the strength of the natural raw rubber, the rubber compound and the vulcanized rubber is higher, and the strength of the general natural rubber can reach three megapascals. The main reason for the high mechanical strength of natural rubber is that it is a self-reinforcing rubber series, which, when stretched, orients the macromolecular chains in the direction of stress to form crystals, which act as reinforcement in the amorphous macromolecular fraction, and the same high strength as that without expansion is due to the close agglomeration of the tiny particles in its internal structure.

Natural rubber is a variety with the best coordination between physical and mechanical properties and processing properties in rubber materials, and is widely applied to the fields of daily life, medical treatment and health, transportation, agriculture, scientific experiments, national defense and the like. With the development of society, people put higher demands on the performance of products, such as: the traditional rubber foaming sole has heavy weight, the wear resistance can not meet the requirement, the heat shrinkage resistance is poor, and the rubber foaming sole is often required to be modified.

The graphene has excellent optical, electrical and mechanical properties, has important application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like, and is considered to be a revolutionary material in the future. In recent years, many studies have been made on modification of rubber materials with graphene, and excellent effects have been obtained. However, in the application process of graphene, the graphene lamellar structure has strong van der waals force or hydrogen bond lamp interaction, so that the graphene lamellar structure is easy to agglomerate and cannot be uniformly and stably dispersed. In general, organic functional groups such as carboxyl, hydroxyl, amino and the like are modified on the surface of the street graphene through chemical grafting, so that the dispersibility of the graphene in a high molecular polymer is improved. However, the method destroys the crystal structure of the graphene, and greatly influences the performance of the graphene.

In addition, the natural rubber foam materials used at present have the following problems:

1. the anti-slip effect is poor, and particularly when the anti-slip rubber is used on ice, the requirements on dry anti-slip and wet anti-slip uniformity are high, and good low-temperature resistance is also required;

2. the mechanical properties such as tensile strength, elongation at break and the like are poor;

3. the wear resistance, the appearance performance and other comprehensive use performances are poor.

Disclosure of Invention

Based on the above situation, the invention aims to provide a graphene natural rubber polymer ice top-slip mixed foam material and a preparation method thereof, which can effectively solve the above problems.

In order to solve the technical problems, the technical scheme provided by the invention is as follows:

a graphene natural rubber polymer ice top-slip mixed foaming material is prepared from the following raw materials in parts by weight:

50-60 parts of natural rubber, 32-37 parts of butyl rubber, 8-12 parts of butadiene rubber, 4-6 parts of white carbon black, 2.4-2.8 parts of basalt fiber, 2-3 parts of nano silicon dioxide, 2.2-2.6 parts of graphene, 1.4-1.7 parts of silicone oil, 1.2-1.5 parts of zinc oxide, 1.5-2.0 parts of zinc stearate, 1.8-2.4 parts of stearic acid, 1.6-1.9 parts of a cross-linking agent, 4.5-5.5 parts of a flow assistant and 1.5-2.0 parts of a foaming agent; the graphene is a multilayer graphene microchip; the cross-linking agent is a mixture of sulfur, dicumyl peroxide and zinc dimethacrylate.

Preferably, the graphene natural rubber polymer ice top-slip mixed foaming material is prepared from the following raw materials in parts by weight: 55 parts of natural rubber, 35 parts of butyl rubber, 10 parts of butadiene rubber, 5 parts of white carbon black, 2.6 parts of basalt fiber, 2.5 parts of nano-silica, 2.4 parts of graphene, 1.5 parts of silicone oil, 1.3 parts of zinc oxide, 1.7 parts of zinc stearate, 2.1 parts of stearic acid, 1.7 parts of a cross-linking agent, 5 parts of a flow aid and 1.8 parts of a foaming agent; the graphene is a multilayer graphene microchip; the cross-linking agent is a mixture of sulfur, dicumyl peroxide and zinc dimethacrylate.

Preferably, the number of the multilayer graphene nanoplatelets is 5-10.

Preferably, the mass ratio of the sulfur to the dicumyl peroxide to the zinc dimethacrylate in the mixture of the sulfur to the dicumyl peroxide to the zinc dimethacrylate is 10: (5-7): (2-3).

Preferably, the white carbon black is silane coupling agent modified white carbon black.

Preferably, the silane coupling agent modified white carbon black is silane coupling agent KH570 modified white carbon black.

Preferably, the zinc oxide is activated zinc oxide.

Preferably, the blowing agent is azodicarbonamide.

Preferably, the flow aid is polyethylene wax.

The invention also provides a preparation method of the graphene natural rubber polymer ice top-slip mixed foam material, which comprises the following steps:

A. respectively weighing natural rubber, butyl rubber, butadiene rubber, white carbon black, basalt fiber, nano silicon dioxide, graphene, silicone oil, zinc oxide, zinc stearate, stearic acid, a cross-linking agent, a flow assistant and a foaming agent according to parts by weight;

B. feeding natural rubber into an internal mixer, masticating for 12-14 min at the temperature of 144-148 ℃, and discharging; storing the masticated natural rubber at room temperature for more than 48h for later use;

C. b, conveying the natural rubber subjected to the mastication treatment in the step B, butyl rubber, butadiene rubber, white carbon black, basalt fiber, nano silicon dioxide, graphene, silicone oil, zinc oxide, zinc stearate, stearic acid and a flow aid into an internal mixer, and internally mixing for 11-14 min at the temperature of 88-92 ℃; then banburying for 8-13 min under the condition that the temperature is 105-110 ℃; then adding a cross-linking agent and a foaming agent, banburying at 122-124 ℃ for 10-12 min, and discharging to obtain a banburying rubber mixture;

D. c, conveying the banburying rubber mixture obtained in the step C into an open mill, thinning for 2-4 times on the open mill, and discharging to obtain an open mill rubber mixture;

E. and finally, feeding the open-mill rubber mixture into a mold for hot-pressing foaming, cooling and molding, and cutting a sample to obtain the graphene natural rubber polymer ice top-slip mixed foaming material.

The graphene natural rubber polymer ice top-slip mixed foaming material is mainly used as a sole material, and the application field of the graphene natural rubber polymer ice top-slip mixed foaming material is not limited to the field of shoe materials, and can also be used in other fields.

Compared with the prior art, the invention has the following advantages and beneficial effects:

the graphene natural rubber polymer ice top-slip mixed foaming material disclosed by the invention is prepared by selecting raw materials, optimizing the content of each raw material, and selecting natural rubber, butyl rubber, butadiene rubber, white carbon black, basalt fiber, nano silicon dioxide, graphene, silicone oil, zinc oxide, zinc stearate, stearic acid, a cross-linking agent, a flow assistant and a foaming agent in a proper proportion, so that the advantages of the raw materials are fully exerted, the raw materials are mutually supplemented and promoted, the prepared graphene natural rubber polymer ice top-slip mixed foaming material is high in slip limiting coefficient (dry slip limiting and wet slip limiting), and good in slip limiting effect; the low-temperature resistance is good, so that the graphene natural rubber polymer ice anti-skidding mixed foaming material has a good anti-skidding effect in the high-temperature environment such as ice surface and the like; the tensile strength is high, the mechanical property is good, and the durability is good; low abrasion, good wear resistance and long service life.

In the graphene natural rubber polymer ice top-slip mixed foam material, natural rubber is used as a main base material.

The graphene natural rubber polymer ice anti-slip mixed foam material has the advantages of fully playing respective advantages, supplementing each other and promoting each other by adding a proper amount of butyl rubber and butadiene rubber, has a similar molecular structure with natural rubber, and has good compatibility, and the anti-slip effect (anti-slip property), the low temperature resistance and the low temperature anti-slip property of the graphene natural rubber polymer ice anti-slip mixed foam material are ensured.

Adding a proper amount of white carbon black and silane coupling agent modified white carbon black; in the raw material system, the compatibility is good, the graphene natural rubber polymer ice anti-skidding mixed foaming material is matched with other components to play a good synergistic effect, the graphene natural rubber polymer ice anti-skidding mixed foaming material can play a remarkable reinforcing role, and the comprehensive mechanical properties such as tensile strength and the like are improved.

The graphene natural rubber polymer ice anti-skidding mixed foaming material disclosed by the invention has the advantages that the basalt fiber and the nano silicon dioxide are added in a proper amount, the compatibility is good, the basalt fiber and the nano silicon dioxide are matched with other components, a good synergistic effect is achieved, the wear resistance, the tensile strength and the like of the graphene natural rubber polymer ice anti-skidding mixed foaming material disclosed by the invention are improved, and the anti-skidding effect (anti-skidding property) of the graphene natural rubber polymer ice anti-skidding mixed foaming material disclosed by the invention can be obviously improved.

Adding a proper amount of graphene, wherein the graphene is a multilayer graphene microchip; according to the formula, the graphene is good in identity with other components, easy to disperse uniformly, complete in structure and good in performance, and has a great effect on improving the anti-skid effect and the mechanical property.

Adding a proper amount of cross-linking agent, wherein the cross-linking agent is a mixture of sulfur, dicumyl peroxide and zinc dimethacrylate. The zinc dimethacrylate plays a role in assisting crosslinking, and the sulfur and dicumyl peroxide (peroxide crosslinking agent) are used as a composite crosslinking agent, so that the graphene natural rubber polymer ice top-slipping mixed foaming material disclosed by the invention is rapidly crosslinked, is moderate in crosslinking, is uniformly distributed in a crosslinking area, and ensures that the foamed graphene natural rubber polymer ice top-slipping mixed foaming material is low in compression permanent deformation rate and good in rebound resilience; the mechanical properties such as tensile strength, elongation at break and the like are good, and the mechanical properties are excellent.

The preparation method has simple process and simple and convenient operation, and saves manpower and equipment cost.

Detailed Description

In order that those skilled in the art will better understand the technical solutions of the present invention, the following description of the preferred embodiments of the present invention is provided in connection with specific examples, which should not be construed as limiting the present patent.

The test methods or test methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials, unless otherwise indicated, are conventionally obtained commercially or prepared by conventional methods.